Tricyclic ketone insecticides and process therefor



United States Patent 3,331,860 TRICYCLIC KETONE INSECTICIDES AND PROCESS THEREFOR Paul E. Hoch, Youngstown, N.Y., assignor to Hooker Chemical Corporation, Niagara Falls, N.Y., a corporation of New York No Drawing. Filed Dec. 2, 1963, Ser. No. 327,519 15 Claims. (Cl. 260-3461) This invention relates to new compositions of matter and to processes for their preparation. More specifically the present invention is of novel tricyclic ketones, pesticidal compositions thereof, a novel cyclization reaction for production of these ketones and methods for controlling pests, utilizing these compounds.

In accordance with this invention, the novel tricyclic wherein X X X and X are independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl,

halogenated alkyl, and halogenated alkenyl; X is selected from the group consisting of hydrogen and halogen; X is a halogen atom; R and R are independently selected from the group consisting of hydrogen, alkyl, and halogenated alkyl; and n is a number from 0 to about 4; at least two of said X X X and X substituents being halogen.

Illustrative examples of the alkyl substituents, which usually contain from 1 to about 18 carbon atoms, and preferably from 1 to about 6 carbon atoms, are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, dodecyl, pentadecyl, stearyl, octadecyl and the like, said alkyl group being a monovalent radical derivable from an aliphatic hydrocarbon by the removal of one hydrogen atom. The alkyl radical can be substituted by halogen, such as chlorine, bromine, fluorine, or iodine, as in chloromethyl, dichloromethyl, trichloromethyl, tn'fluoromethyl, bromoethyl, chloroethyl, fluoropropyl, hexachloroisopropyl, chlorobutyl, bromobutyl, chlorocyclohexyl, iodopropyl, bromooctyl, chlorooctyl, chlorodecyl, iododecyl, chlorododecyl, bromododecyl, bromopentadecyl, iodooctyl and the like.

Among the alkenyl substitutents which usually contain from 1 to about 18 carbon atoms and preferably, from 1 to about 6 carbon atoms, are vinyl, allyl, butenyl, hexenyl, octenyl, dodecenyl, and the like, said alkenyl being a radical derivable from an alkene by the removal of one hydrogen atom. The alkenyl radical can be substituted by halogen, such as in tricblorovinyl, 2-chloroally1, 2,3-difluorobutenyl, 2,3-dichlorododecenyl and the like.

The substituting halogen atoms which are useful include chlorine, bromine, fluorine, and iodine, and the halogen ated alkyl or alkenyl radical may bear from one halogen up to a number corresponding to perhalogenation.

The substituent X as represented, is written with the bond unattached to any particular carbon atom to 7 indicate that the n halogen atoms X may be located on any of the substitutable positions, in place of hydrogen atoms. substitutable position is being employed herein to mean any carbon atom in the generic formula which, if n were zero, would hear one or more hydrogen atoms.

When n is other than zero, the compounds of the invention are prepared by a process involving a substitutive halogenation step (described in more detail hereinafter) which introduces the n halogen atoms into the various available substitutable position. It will :be seen that, in formulas given, n hydrogens will be shown for the sake of clarity, although they are replaced by X substituents. This is done because, to remove the hydrogens would specify the place of substitution, which maynot be intended.

The present invention encompasses mixtures which result from the introduction of n halogen atoms X into the available substitutable positions. Such mixtures represent the most economical and commercial products. In these mixtures n generally represents an average value and in some instances these mixtures may contain components with more than n halogen atoms. Although the mixtures are complex, pure isomers have been separated therefrom, as will be more fully described subsequently.

The preferred compounds for insecticidal activity and ease of preparation, are those wherein the X X X X X and X substituents are chlorine or bromine, R and R are hydrogen and n is a number from 0 to about 3. Even more preferred are those compounds of the preferred group wherein the halogen is chlorine.

Some of the novel compounds embraced within the present invention are, for example:

H CHCH:

H C1 H CHCH5 Br H CH(O H2) H Br H Cl H CH(C-1Hg) Cl H CHCHa CHCH:

are the following:

Since each of these compounds contains at least one asymmetric carbon atom, each can exist in more than one stereoisomeric form. The products of the invention are generally mixtures of stereoisomers, which, in some instances, can be separated but in other instances resist separation. This invention includes both mixtures and separable isomers. Interconversion, equilibration, or epimerization of various of the stereoisomers, when they are dissolved in ionizing solvents, has been observed, making it more desirable to deal with the products as mixtures rather than as separated isomers.

The novel carbonyl compounds of the present invention may be prepared from novel polyhalogen-containing bicyclic compounds. These novel reactants are disclosed in copending application Ser. No. 413,947, filed Nov. 25, 1964.

The reaction occurring canbe illustrated by the following sequence of equations which are not intended to be limiting.

wherein M is a cation, preferably of an alkali metal such as lithium, sodium, potassium, and the like; R is selected from the group consisting of hydrogen, aryl, substituted aryl, alicyclic, substituted alkyl and alkyl radicals and the remaining substituents X X X X X X, R and R are as described herein, and where X? is halogen.

The diol starting reactant to be utilized for reaction (1) can be prepared by the process as disclosed in US. 3,007,958 wherein is detailed the preparation of compounds where X X X X X and X are chlorine.

The analogous diols, wherein X X X X and X are other than chlorine and Where R and R are other than hydrogen are prepared by a similar reaction of the appropriate substituted cyclopentadiene and butenediol as represented by the following:

Suitable cyclopentadienes include, for example l,2,3,4,5- pentachlorocyclopentadiene, 1,2,4,5,5 pentachlorocyclopentadiene, tetrachlorocyclopentadiene, 1,2,3,4-tetrachloro-S,S-dibromocyclopentadiene, trichloromethylpentachlorocyclopentadiene, trichlorovinylpentachlorocyclopentadiene, butenylpentachlorocyclopentadiene, and the like. Among the diols are for example Z-butene-l, 4-diol (preferably cis), 3-hexene-2,5-diol, 8-hexadecene-7,10-diol,1,4- cyclohexyl-2-butene 1,4-diol' and the like. The reaction conditions for efiecting this reaction are essentially those.

described in US. 3,007,958.

Reaction (1) is accomplished by contacting the indicated bicyclic diol with a strong base in an alcohol or an aqueous alcohol medium. The base to be selected is capable of forming the alkoxide of the alcohol, such as the sodium, potassium alkoxide, or the like. If desired, the alkoxide reactant can be prepared prior to its addition to the diol. V Because the R" substituent is removed by reaction (2) the nature of R is not particularly important. However R will generally be an alkyl radical from 1 to about'ZO carbon atoms and preferably of from 1 to about 6 carbon atoms such as methyl, ethyl, propyl, Z-hydroxyethyl and the like.

R" can also be hydrogen, this being accomplished either by conducting reaction (1) in a solvent system containing suflicient water, or by gentle acid hydrolysis of the corresponding compounds where R is alkyl. By gentle acid hydrolysis is meant the exposure of the product where R is alkyl, to a mineral acid such as sulfuric acid at a lower concentration, lower temperature, and/ or shorter time than is required for reaction (2) to occur. The compounds where R" is hydrogen may be used as intermediates in reaction (2). l p

However, R" may also be substituted alkyl of from one to about twenty carbon atoms and preferably of from one to about six carbon atoms, said alkyl group being substituted by halogen, like chlorine, bromine, fluorine, iodine, hydroxyl, alkyl, and aryl; aryl of from six to about fourteen carbon atoms and preferably of from six to ten carbon atoms, such as phenyl, naphthyl, anthracyl, and the like; substituted aryl of from six to about fourteen carbon atoms and preferably of from six to about ten carbon atoms, said aryl group being substituted by halogen, hydroxyl, alkyl, substituted alkyl and the like; and, alicyclic of from three to about twelve carbon atoms and preferably of from three to about six carbon atoms, such as cyclohexyl, cyclopropyl, cyclopentyl, cycloheptyl, cyclooctyl, and the like.

The process of the present invention is represented by reactions (2) and (3). Reaction (2) is effected preferably in the liquid phase and in the presence of a strong acid, preferably a mineral acid. While an acid-resistant solvent which is miscible with the acid can be used, e.g., nitrobenzene, it is not necessary to use a solvent since the mineral acid itself can perform this solvent function. A preferred mineral acid is concentrated sulfuric acid (preferably 80-100%) which functions as both a solvent and as a catalyst for reaction (2). Other strong mineral acids such as hydrochloric can also be employed. Reaction (2) is accomplished at a temperature of from about degrees centigrade to about 150 degrees centigrade and preferably from about 40 centigrade to 120 centigrade. Atmospheric pressure is suitable and most convenient, although subor super-atmospheric pressures can be employed. The reaction time is from several minutes to several days and preferably from about A hour to about 50 hours, depending somewhat on the temperature selected.

The product of reaction (2) can be isolated by any one of several methods known in this art, such as by diluting the acid medium, when sulfuric acid is used, to cause precipitation, followed by filtration of the product. The product can also be extracted by using an organic solvent which is resistant to acid, such as benzene, aliphatic and aromatic chlorohydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzenes, ethylene dichloride, trichloroethylene, perchloroethylene, nitromethane and the like.

The products of reaction (2) represents the novel compounds of this invention wherein n is equal to zero. These compounds are useful per se because they possess a substantial degree of pesticidal, especially insecticidal, activity. The compounds are most useful as intermediates for further halogenation to products wherein n is greater than zero. Such halogenated products have high insecticidal activity.

The products of reaction (2) are often mixtures of stereoisomers probably because of isomerism at the carbon substituted by X although we do not wish to be limited by this theory. These mixtures are useful per se but, if desired, can be resolved into their isomer components by fractional crystallization or other means known in the art.

Reaction (3), the halogenation step, is best effected as a direct halogenation when X is chlorine. When X is other than chlorine, it is most practical to introduce n chlorine atoms and then replace these by the desired halogen, as by exposure of the chlorinated intermediate to an appropriate reagent, for example sodium iodide in acetone, potassium fluoride in dimethyl formamide, hydrogen bromide in glacial acetic acid, or the like.

The chlorination of the products of reaction (2) is conducted conveniently by passing elemental chlorine or a chlorine-donating reagent, such as sulfuryl chloride, phosphorus pentachloride, an N-chloroamide, or other positive chlorine compound into the product of reaction (2) in a suitable react-ion medium.

The temperature for effecting reaction (3) is from about 40 degrees centigrade to 180 degrees centigrade, and preferably of from about 20 degrees centigrade to degrees centigrade. When the product of reaction (2) melts low enough, it may be chlorinated without a solvent. Among the solvents which may be used for the chlorination are those organic solvents which are resistant to chlorine such as carbon tetrachloride, chlorinated benzenes, tetrachloroethane and the like. Other solvents include halogen resistant inorganic liquids such as thionyl chloride or phosphorus oxychloride.

The chlorination reaction can be efiiected without a catalyst but a free radical catalyst can be utilized for accelerating the reaction. These include actinic light, benzoyl peroxide, or other organic peroxides, azobisisobutyronitrile and the like.

The desired level of chlorination at which the reaction may be halted is detected by methods known in this art such as by measuring the amount of chlorine introduced, noting the change in weight of the product, or by measuring the amount of hydrogen chloride released.

This reaction is convenienly conducted at or near atmospheric pressure, but subor super-atmospheric pressures can be used.

To further illustrate the preferred novel compounds and process of this invention, the following specific nonlimiting equations are given:

(4) Cl: H CHQOH Cl H o1 CH2OH J l 9:11 I C Cir 01 01 l CHaOH H CHzOH Cl H o1 CHzOH 0012 NaOCHs 01 oHion Cl H CH3o 0 Cl CH2OH ll H O -CH (6) H Cl\H CHBO- i *CHtOH Hzsoi 01 (I301,

O-CH2 Cl H CH2 c on o H l H\CH2/ (7) Cl H CH2 C17 H C01; 0 XL. 0:

/ Cl H CHz Cl H CH2 11 c BLT on o 0..

/\ Cl H CHz The compounds of this invention are insecticides having a very high level of activity on important insect pests, such as flies, mosquitoes, army worms, corn borers, other lepidopterous larvae, aphids, and other economic invertebrate pests. The compounds of this invention also possess activity againstrsnails, slugs, millipedes, silverfish, and nematodes. Activity of a useful level is also found on rodent pests such as rats, mice, and moles.

A further advantage of the novel compounds of this invention is that, in contrast to the prior art chlorinated insecticides such as DDT, BHC, dieldrin, aldrin, eudrin,

and related compounds, they leave Significantly lesser amounts of toxic residues in crops and soils. This characteristic permits use of the claimed compounds closer to harvest than would be possible with chlorocarbons of long persistance, and extends greatly the range of usefulness of the claimed compound for food crops, tobacco, and forage, in comparison to other chlorinated insecticides of the prior art.

An additional advantage of the products of this invention is in the variety of formulations in which they may be utilized for insecticidal use, generally in an amount of 0.5 part to 1000 parts by Weight of the compound of this invention to about 1 to 1000 parts by weight of other insecticides. It is, of course, appreciated that various effective amounts of the compounds of this invention can be utilized, and the application rates will often be dependent on the particular circumstances. For example, the puri fied or crude products may be combined with other biocides or pesticides, including insecticides, such as DDT, methoxychlor, lindane, aldrin, endrin, DDD, BHC, parathion, malathion, methyl parathion, lead arsenate, calcium arsenate, rotenone, allethrin, pyrethrum, nicotine, summer oils, dormant oils, dinitroalkylphenols, dinitrocresols, chlordane, heptachlor, insecticidal carbamates and organophosphates; chlorinated terpenes, demeton, thiophosphates and dithiophosphates such as 0,0-dimethyl S-oxo- 1,2,3 benzotriazin 3 (4H) ylmethylphosphorodithioate; 0,0 diethyl (2 isopropyl 6 methyl 4 pyrimidinyl)phosphorothioate; dimethyl 2,2-diclrlorovinyl phosphate; miticides such as bis(pentachlorocylopentadienyl) chlorinated arylsulfonates, chlorinated diarylsulfones and the like, fungicides such as sulfur, dithiocarbamates and N trichloromethylthio 4 cyclohexene 1,2 dicarboximide to list but a few. Other insecticides with which the compounds of the invention may be employed are those listed by Kenaga, Bull. Ent. Soc. America, 9, 69 ff (1963) It' may also be desirable to combine the insecticidal products of this invention with a class of potentiators or, synergists known in the insecticidal art as knockdown agents, although against most insects the compounds of the present invention possess an excellent rate of action by themselves. Among the large number of synergists and knockdown agents which may be used for this purpose are the organic thiocyanates and others listed by Kenaga (10c. cit., pp. 69, 70, 92). Other adjuvants useful with the compounds of the invention include odorants, colorants, stabilizers, and extending agents (vapor pressure depressants and non-volatile solvent substances such as chlorinated waxes, resins, and the like).

Another advantage of the inventive compositions is that they may readly be formulated as solids or liquids using solid or liquid solvent vehicles, carriers, or extenders. Suitable diluents are solids or liquids of an inert nature. Illustrative solid diluents include among many others: sawdust, vermiculite, clay, tales, flours, silicas, alkaline earth carbonates, oxides and phosphates, solid fertilizer, and the like. Suitable solvents for liquid formulations include ketones, aromatic and aliphatic hydrocarbons and petroleum fractions or distillates such as Xylenes, aromatic naphthas, and the like.

Whether dissolved or dispersed, suspended or emulsified in a liquid or formulated as a dust or powder or some other solid preparation the insecticides of this invention may advantageously contain one or more substances known or referred to variously as modifiers, wetting agents, or surface-active agents. Suitable agents are .alkylaryl sulfonates, polyoxyethylene polyol ethers and esters, and the like.

The compounds of the invention can also be formulated in bait compositions, for example with fatty, sugary, or proteinaceous ingestible bait substances.

For controlling pests the compounds of the present invention are applied in insecticidal quantities or effective amounts onto the site of the existing or anticipated harmful pests. Effective insecticidal concentrations arein the range of from about 0.01 pound per acre to about 20 pounds per acre. In most crop applications rates of 0.05 to 5 pounds per acre are employed. Lower rates are used on very susceptible species, such as mosquito larvae, while higher rates are used on extremely resistant species. Higher rates than 20 pounds per acre may be used where economics permits.

a The rate to be used will depend on many variables such as the insect species, duration of control desired, weather, soil type, crop species, timing between application and harvest, economics and other factors known to one of skill in this art. The application of the insecticide may be to the crop itself or to the soil in which it is grown.

In the specification, examples and claims, parts are by weight and temperatures are in degrees centigrade, unless otherwise indicated.

In order that those skilled in the art may better understand the present invention and the manner in which it may be practiced, the following illustrative examples are given.

Example 1 remaining slurry was poured into three volumes of water,

causing the inorganic salts to dissolve and the organic product to precipitate. The product was filtered, washed with water, and dried in an oven to obtain a substantially theoretical yield of the crude product having elemental analysis and spectroscopic properties for o--'-0H, Recrystallization of this crude product from hot carbon tetrachloride yielded a pure product, with a melting point of 157 to 158 degrees centigrade.

Example 2 To 6800 parts of concentrated (97%) sulfuric acid at 93 to 95 degrees centigrade were added with stirring 750 parts of the product of Example 1. The mixture was heated at 95 degrees centigrade for 5 hours and then cooled to room temperature. The solution was poured slowly into cold water with stirring. The precipitated solid was filtered out, washed with water, and dried to obtain a gray solid in 89.5 percent of the theoretical yield. The

' material, a mixture of isomers, had a melting point in the vicinity of 19 8 degrees centigrade to 204 degrees centigrade. It had the correct elemental analysis for C H O Cl The infrared spectrum shows a strong ether band at 1060 cm.- a ketone carbonyl band at 1785 cm.- and methylene CH bands at 1480 cmf and no -OH bands. The structure is therefore believed to. be

The crude product can be used for the further chlorination.

Example 3 The tricyclic ketone produced in Example 2 was resolved into two isomers by the following procedure. 611 parts of the product of Example 2 were recrystallized from 2000 parts of ethanol. The solids were then recrystallized from carbon tetrachloride to obtain one of the stereoisomers, melting point 196 degrees Centigrade to 195 degrees Centigrade. This isomer is distinguishable from the other described below by the fact that the former possesses an infrared absorption band at 12.1;r, whereas the latter possesses, instead, an absorption band at 12.4, (oberved in Nujol mull). These isomers of C H O Cl are hereinafter designated the 12.1,a isomer and the 124 isomer. They are believed to be stereoisomeric at the carbon bearing X (:Cl) but it is not intended to be limited by this theory.

The second stereoisomer, the 12.4,; isomer was obtained by collecting a second crop of crystals by cooling and partial evaporation of the ethanol mother liquor from the above-described crystallization, and then recrystallizing this substance several times from heptane. This 12.4;1. isomer has a melting point of about 217-220 degrees centigrade somewhat variable due to decomposition which appears to be promoted by traces of impurities. Both isomers have the correct percentage chlorine (54.7%) for C9H7O2Cl5 and exhibit a ketone in the infrared spectrum and 21 C0 bond (ether), but no O-H bonds. The corresponding bromine compound is prepared by subjecting the product of Example 3 to reaction with sodium bromide resulting in the product C H O Cl Br Example 4.Chl0rinati0n of crude C H O Cl A solution of 164 parts of the crude C H O Cl of Example 2 in 300 parts of refluxing carbon tetrachloride (80 C.) is exposed to the light from a mercury vapor temperature, and chlorine gas is passed in with stirring. The extent of the chlorination is measured by collecting the evolved hydrogen chloride in water and titrating the hydrochloric acid from time to time.

When 1, 2, 2 /2, 3, and 4 moles of hydrogen chloride are collected per mole of C H- O C1 in the system (corresponding to 1, 2, 2 /2, 3 and 4 Cl introduced per mole), portions of the reaction mixture are removed and evaporated under -25 mm. vacuum to remove solvent and dissolved gases. The products are obtained as residues and have the following characteristics:

n (Cl/mole) Percent 01 Percent 01 Physical Characteristics Calculated Found 1 59. 3 58. 2 Yellowish-tan semi-solid. 2 63. 1 63.0 Do. 2. 5 64. 8 64. 8 Do. 3 66. 4 66. 5 D0. 4 68. 2 67. 5 Syrup.

Example 5 n or n CHCI 01- con 0 or H CHOl On evaporation the crystallization mother liquors yielded a syrup of the same elemental analysis, indicating other isomers to have been in the crude product.

Example 6 Under conditions like those of Example 5, the 12.4a isomer was chlorinated to introduce two additional chlorine atoms per mole. The product was a yellowish semisolid which, on repeated recrystallization from hexane, yielded a crystalline isomer, melting at 1295-1315 degrees centrigrade and being of the correct elemental analysis for C H O Cl The absence of methylene absorption bonds in the infrared spectrum indicates that this compound has the structure The corresponding bromine analog is prepared by subjecting the chlorinated product of Example 6 to a reaction with hydrogen bromide which results in the product On evaporation the recrystallization mother liquors yielded a syrup of the same elemental analysis, indicating that other isomers were present in the crude in addition to the crystalline isomer.

Example 7.-Emulsifiable formulation The following were blended by mixing:

Pounds Product of Example 4 (n=2) 1.25 Emulsifier (Emcol H500X, a blended sulfonate-polyoxyethylene ether) 0.25

Xylene, to 1 gallon total volume.

The concentrate was emulsifiable with water (about a 5% solution) and the resultant emulsions are sprayed at the rate of 0.1-1 pound of active ingredient per acre onto cabbage plants to obtain satisfactory control of cabbage loopers and aphids.

Example 8.Granular formulation A solution of 1 part of the product of Example 4 (2 Cl/mole) in 1 part of heavy aromatic naphtha was sprayed onto 8 parts of 10-30 mesh attapulgus clay granules while tumbling the granules. There resulted a free-flowing granular solid formulation.

The powdered formulation is applied as a side dressing at the rate of 0.25 pound of insecticide per acre on tomato plants for satisfactory control of lepidopterous larvae.

Example 9.-Dust formulation Adult houseflies (Musca domestica) were sprayed with aqueous dispersions of several of the compounds of the invention and with DDT for comparison. The knockdown percentages after two hours were noted and the mortality percentages after 24 hours were recorded. The results are as follows:

. 2hr. 24 hr. Compound Cone. Knock- Kill,

(p.p.rn.) down, Percent Percent H 01 H CH2 1,000 100 100 C1 Cl H CH2 /Cl\H/CH; Cl 2 igg 13 1 01 i X 0.5 10 40 C012 0 0.25 0 0 Cl H CH2 H 01 H OH? 011 2 100 100 C1 1 100 100 0.5 100 100 C011 0 0.25 50 90 0:

Cl H CH2- (isomer mixture) H Cl H CH2 C125 2 100 100 X 1 100 100 o1 H on:

H 01 H CH2 C13 2 100 100 01 1 70 100 0.5 0 60 7 C012 0 0.25 0 10 Cl H CH:

DDT 2 0 0 1 0 0 0.5 0 0 0.25 0 0 Example 11.Activity on Southern army worm Larvae of the Southern armyworm (Prodenia eridania) were sprayed with aqueous dispersions of the compounds of the invention. The percentages of kill after 24 hours were noted, the results being as follows:

' While there have been described various embodiments of the invention, the methods and elements described are not intended to be understood as limiting the scope of the invention, as it is realized that changes therewithin are 12 possible, and it is further intended that each element recited in any of the following claims is to be understood as referring to all equivalent elements for accomplishing substantially the same results in substantially the same or equivalent manner, it being intended to cover the invention broadly in whatever form its principle may be utilized.

What is claimed is: 1. A tricyclic ketone of the formula X1 H CHR X n X H CHR wherein X X X and X are selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl; said alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl containing from 1 to about 18 carbon atoms;

X is selected from the group consisting of hydrogen and halogen.

X is a halogen atom; R and R are selected from the group consisting of hydrogen, alkyl of from 1 to about 18 carbon atoms, and halogenated alkyl of from 1 to about 18 carbon atoms; n is a number from 0 to 4; at least two oi said X X X and X substituents being halogen.

2. A tricyclic ketone of the formula CHR1 X25 wherein X X X X X and X are halogen; R and R are hydrogen; and n is a number from 0 to 4.

3. A compound of the formula H X H CH2 Cln w x OX2 O wherein X is a halogen atom and n is a number from 0 to 4.

4. A compound of the formula H Cl H CH2 0 on 0 i/ Cl H CH2 5. A compound of the formula H Cl\H/C Hz 015 X X (I) Cl: /0 Q or H on,

where n is a number from 0 to 4.

6. A compound of the formula 1 3 8. A compound of the formula (I'JI\H/CH:\ CI3 H CljiT G1: //O l oi H om 9. A compound of the formula 01 H CHCl H Cl C on 0 C1 H CH 01 10. A process for the preparation of the compounds of claim 2 which comprises (1) reacting a compound of the formula O--OHR with a strong acid to produce H CHRI (2) subjecting the compound produced in step (1) to a chlorination, followed by (3) replacement of the chlorine atoms with the desired halogen, wherein X X X and X are selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl, and R and R are selected from the group consisting of hydrogen, alkyl, and halogenated alkyl the foregoing alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl radicals containing from 1 to about 18 carbon atoms; X is selected from the group consisting of hydrogen and halogen; and R" is selected from the group consisting of hydrogen, alkyl and substituted alkyl of 1 to 20 carbon atoms, a-licyclic of 3 to 12 carbon atoms, and substituted aryl of from 6 to 14 carbon atoms wherein aryl is selected from the group consisting of monocarbocyclic aryl, dicarbocyclic aryl and tricarbocyclic aryl at least two of said X X X and X substituents being halogen.

11. A process for the preparation of the compound of claim 2 which comprises (1) reacting a compound of the formula O C'HR with a strong acid at a temperature of from degrees centigrade to about 150 degrees centigrade to produce H CHE X H CHR selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl; R and R are selected from the group consisting of hydrogen, alkyl, and halogenated alkyl the foregoing alkyl, alkenyl, halogenated alkyl, and halogenated alkenyl radicals containing from 1 to about 18 carbon atoms; X is selected from the group consisting of hydrogen and halogen; and R" is selected from the group consisting of hydrogen, alkyl and substituted alkyl of 1 to 20 carbon atoms, alicyclic of 3 to 12 carbon atoms, and substituted aryl of from 6 to 14 carbon atoms w-herein aryl is selected from the group consisting of monocarbocyclic aryl, dicarbocyclic aryl and tricarbocyclic aryl; n is a number from 0 to 4; at least two of said X X, X and X' substituents being halogen.

12. A process in accordance with claim 11 wherein the strong acid is sulfuric acid.

13. A process in accordance with claim 11 wherein n is zero which comprises (1) reacting a 'bicyclic diol of the formula x OHR OH 1 X I} CHR OH with a compound of the formula MOR" to produce H X1 H CHR1OH R"O OOHR2 (2) followed by reaction of the compound of step (1) with a strong acid, wherein X is selected from the group consisting of hydrogen and halogen, M is a metallic cation and all other radicals are as defined in claim 11.

14. A process for the preparation of a tricyclic ketone of the formula which comprises reacting an ether alcohol compound of the formula 15 wherein n is a number from 1 to 4; which comprises (1) reacting an ether alcohol of the structure degrees centigrade until the desired conversion to the ketone has occurred, followed by the isolation of said ketone; (2) and, when n is to be greater than zero, treating Y the ketone of step (1) with at least n molar equivalents of a chlorinating agent.

References Cited UNITED STATES PATENTS 2,861,919 11/1958 Gilbert 167-33 2,974,084 3/1961 Mayhew et al l67-33 3,036,092 5/1962 Phillips et a1. 260346.2 3,076,818 2/1963 Graham et a1 260-3462 OTHER REFERENCES Fieser: Organic Chemistry, page 32, Second Edition (1950).

NICHOLAS S. RIZZO, Primary Examiner.

H. R. JILES, Assistant Examiner. 

1. A TRICYCLIC KETONE OF THE FORMULA 